Modified polyurethane liquid polymer compositions

ABSTRACT

A novel, heat curable, liquid polymer composition is disclosed which comprises a modified polyurethane oligomer containing terminal ethylenic unsaturation, a free radical generating catalyst, and at least one additional component selected from a reinforcing agent and a filler. The cured composition demonstrates desirable impact properties and is particularly useful in automotive body constructions.

This application is a continuation-in-part of copending application Ser. No. 467,005, filed Feb. 16, 1983, now abandoned, which is a division of application Ser. No. 306,848, filed Sept. 29, 1981, now U.S. Pat. No. 4,439,576, which in turn is a continuation-in-part of application Ser. No. 203,212, filed Nov. 3, 1980, now abandoned, and of application Ser. No. 203,213, which was also filed Nov. 3, 1980, and now abandoned.

In recent years, there has been a steady increase in the use of reinforced plastic materials for exterior components in automotive construction. Further increases in the utilization of plastics can be expected as automobile manufacturers continue to strive to meet vehicle weight reduction goals.

In the area of rigid plastic automotive components, fiberglass reinforced thermosetting polyester resins have been extensively employed. This can be attributed to their overall physical capabilities (e.g., dimensional stability, strength, high temperature resistance and paint adhesion). Other advantages include facility of handling and machining. However, these polyester systems still present certain deficiencies such as a brittle nature, which can lead to severe impact and fatigue problems. There is also a need to improve surface characteristics and shrinkage control.

To overcome these problems, various additives have been introduced into polyester sheet molding compounds (SMC) and bulk molding compounds (BMC). For example, in U.S. Pat. No. 4,020,036 issued to Aubrey South, Jr. on Apr. 26, 1977, liquid polymers, such as polybutadiene, are added in order to toughen polyester products. However, since these materials are not inherently compatible with polyester, these additives cannot be added to the polyester until it is time to mix the resin with the fiberglass. Saturated diacids or long-chain glycols also have been used in preparing polyester resins; the resulting products have been flexibilized, but, at the cost of lower mechanical and thermal properties.

Another approach involves the introduction of polyurethane systems into polyester resins. In U.S. Pat. No. 4,062,826 issued to Francis Gowland Hutchinson et al. on Dec. 13, 1977, precursors of a cross-linked polyurethane are polymerized within a mixture of ethylenically unsaturated polyester and vinyl monomer to form a product with an interpenetrating polyurethane get network within the polyester cross-linked structure. While higher impact properties are reported to be achieved, the fine surface finish required for automotive body part applications is not accomplished. See Forger, G., Toughened SMC, Plastics World, page 63 (June 1978).

Now, according to the invention, it has been discovered that these requirements can be achieved by employing a select polyurethane system which includes a select polyurethane oligomer, a free radical generating catalyst and at least one additional component selected from a reinforcing agent and a filler. In the practice of the invention, a molded plastic product is produced which features desirable impact properties and is suitable for many of the same utilities as thermoset polyester resin compositions such as parts for automotive body applications.

The polyurethane oligomer that is utilized according to the invention is prepared by reacting an organic polyisocyanate, a polyol reactant and an isocyanate reactive group-containing unsaturated monomer. The reaction is carried out using methods well known in the art and employing such relative proportions of the reactants so as to achieve an oligomer product having an equivalent ratio of NCO to OH from about 0.8/1 to about 2/1, and preferably from about 1/1 to about 1.2/1. In forming the oligomer, there is also employed an equivalent ratio of isocyanate reactive group-containing unsaturated monomer to polyol reactant in the range from about 0.6/1 to about 3/1, and preferably from about 0.8/1 to about 2/1. By reaction of the organic polyisocyanate, polyol reactant and isocyanate reactive group-containing unsaturated monomer, a controlled molecular weight polyurethane oligomer with terminal reactive unsaturation is produced.

Preferably, the reaction is accelerated by employing a catalyst; common urethane catalysts, e.g., tertiary amines and metal compounds such as stannous octoate or dibutyltin dilaurate may be used. Any catalytic amount may be employed; illustratively, such amount varies, depending on the particular catalyst utilized, from about 0.01 to about 1 percent by weight of the polyurethane oligomer. It is also preferred to carry out the reaction in the presence of a reactive copolymerizable solvent. Suitable copolymerizable solvents include vinylidene compounds such as styrene, vinyl toluene, methacrylic esters, acrylic esters, divinyl benzene, and the like, familiar to those skilled in the art. The amount of copolymerizable solvent employed may be varied over a wide range. Generally, however, the copolymerizable solvent is employed in an amount of from about 0 to about 100 parts by weight per 100 parts by weight of the polyurethane oligomer of the present invention.

Any suitable organic polyisocyanate, or mixture of polyisocyanates, may be employed in preparing the polyurethane oligomer. Illustrative are toluene diisocyanate, such as the 80:20 and the 65:35 mixtures of the 2,4- and 2,6-isomers, ethylene diisocyanate, propylene diisocyanate, methylene-bis(4-phenyl)isocyanate, xylene diisocyanate, 3,3'-bitoluene-4,4'-diisocyanate, hexamethylene diisocyanate, naphthalene-1,5-diisocyanate, the polymeric isocyanates such as polyphenylene polymethylene isocyanate, mixtures thereof, and the like. In accordance with a particularly preferred embodiment of the invention, there is employed an isomeric mixture of 2,4- and 2,6-toluene diisocyanate in which the weight ratio of the 2,4-isomer to the 2,6-isomer is from about 60:40 to about 90:10, and more preferably from about 65:35 to about 80:20.

The polyol reactant used in the polyurethane oligomer formation comprises a select combination of polyols, i.e., a high functionality polyol and a chain extender. More in detail, the high functionality polyol is selected from polyether polyols and mixtures of two or more such compounds. The high functionality polyol, or mixture of high functionality polyols, should have an average equivalent weight ranging from about 75 to about 500. Preferably, the average equivalent weight is about 75 to about 350, and more preferably about 90 to about 200. The average functionality of the high functionality polyol or high functionality polyol blend is at least about 3, preferably about 3 to about 8, and more preferably about 3.3 to about 6.

Suitable high functionality polyether polyols include various polyoxyalkylene polyols and mixtures thereof. These can be prepared, according to well-known methods, by condensing an alkylene oxide, or a mixture of alkylene oxides using random or step-wise addition, with a polyhydric initiator or a mixture of polyhydric initiators. Illustrative alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides such as styrene oxide, and the halogenated alkylene oxides such as trichlorobutylene oxide and so forth. The most preferred alkylene oxide is propylene oxide or a mixture thereof with ethylene oxide using random or step-wise oxyalkylation.

The polyhydric initiator used in preparing the high functionality polyether polyol comprises a carbohydrate or a carbohydrate derivative. Illustrative are sucrose, dextrose, methyl glucoside and mixtures thereof. In a particularly preferred embodiment, the polyhydric initiator includes a mixture of a carbohydrate or a carbohydrate derivative with at least one aliphatic diol or triol. Exemplificative of the latter are water, ethylene glycol, propylene glycol, the butylene glycols, glycerol, trimethylolpropane, triethylolpropane, the alkanolamines, and the like, and mixtures thereof.

The most preferred group of polyhydric initiators for use in preparing the high functionality polyether polyol is one which comprises mixtures of sucrose or dextrose or methyl glucoside with an aliphatic triol, preferably glycerol.

The alkylene oxide-polyhydric initiator condensation reaction is preferably carried out in the presence of a catalyst such as KOH as is well known in the art. In effecting the reaction, a sufficient proportion of alkylene oxide is used as to provide a final polyol product having an average equivalent weight of about 75 to about 500, preferably about 75 to about 350, and more preferably about 90 to about 200. The catalyst is thereafter preferably removed, leaving a high functionality polyether polyol which is ready for use in preparing the polyurethane oligomer of the invention.

As indicated above, in forming the polyurethane oligomer, a chain extender is included in the polyol reactant. These chain extenders have an average equivalent weight ranging from about 31 to about 4,000, preferably from about 31 to about 500, and an average functionality of about 2. Suitable chain extenders include the following and mixtures thereof: (a) low molecular weight diols, such as ethylene glycol, butane diol, pentane diol, hexane diol, 2-ethyl-1,3-hexane diol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, bisphenol A, and the like; and (b) polyether diols, such as propylene oxide diols, propylene oxide-ethylene oxide diols, and the like. Tripropylene glycol, polyether diols having an equivalent weight of about 100 to about 500, and mixtures thereof are particularly preferred. Usually, a proportion of chain extender is employed which ranges from about 20 to about 1,500, and preferably from about 50 to about 900, parts by weight per 100 parts by weight of the high functionality polyol.

Suitable isocyanate reactive group-containing unsaturated monomers include hydroxyalkyl acrylates, hydroxyalkyl methacrylates and hydroxyalkyl acrylamides, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylamide, hydroxypropyl acrylamide, and the like, and mixtures thereof. Hydroxyalkyl acrylates and hydroxyalkyl methacrylates are preferred, with hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate being the most preferred.

The modified polyurethane oligomer liquid polymer system is polymerized and cured in the presence of a heat activated, free radical generating catalyst. The actual curing conditions may vary over wide ranges and are generally dependent on the nature and amount of the particular catalyst employed. Suitable free radical generating catalysts include peroxide or azo type compounds, known to those in the art. Typical peroxide catalysts are illustrated by organo peroxides and hydroperoxides such as benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, t-butylbenzene hydroperoxide, cumene hydroperoxide, t-butyl peroctoate, and the like. Typical azo compounds are azobis-isobutyronitrile, 2-t-butylazo-2-cyano-4-methylpentane, and 4-t-butylazo-4-cyano-valeric acid. The preferred catalysts are peroxide catalysts. In particular, preferred peroxide catalysts are t-butyl peroctoate, t-butyl perbenzoate, and mixtures thereof. Any suitable catalytic amount may be employed; however, the catalyst generally is used in an amount from about 0.1 to about 10 parts by weight per 100 parts by weight of the polyurethane oligomer.

The composition of the present invention also contains at least one of a filler or a reinforcement material. In particularly preferred embodiments of the invention, both filler and reinforcement material are included in the formulation. Any material known to those in the art as being suitable as a filler may be employed. Generally, a variety of materials, e.g., finely divided solids including CaCO₃, clay, alumina, talc, glass microspheres, and the like, may be utilized. Also, any suitable reinforcement material may be used, such as chopped fiberglass, carbon fibers, asbestos fibers, boron nitride whiskers, and the like. The amount of filler generally included in the formulation may vary considerably, but usually ranges from about 20 to about 400 parts, and preferably from about 100 to about 220 parts, per 100 parts by weight of the polyurethane oligomer. When a reinforcing agent is added to the formulation, the amount may also vary over a wide range; however, a typical formulation will generally contain from about 10 to about 150 parts, and preferably from about 60 to about 130 parts, per 100 parts by weight of the polyurethane oligomer.

The composition also may include other standard ingredients, if desired, such as internal mold release agents, e.g., calcium, zinc, magnesium, or sodium stearate. Low shrink or impact additives also may be included, if desired. Pigments, dyes, stabilizers, viscosity modifiers, (e.g., Group II metal oxides and hydroxides, such as magnesium oxide) and various other additives familiar to those skilled in thermosetting polyester technology also may be added.

By way of illustration, all the ingredients of the composition, except filler and/or reinforcing material, are mixed, usually in a high shear mixing device. The filler, if employed, is then added gradually to the mixture and mixed until a homogeneous paste is obtained. Reinforcing agent, such as chopped glass, is then added gradually to the paste and the paste is worked so as to achieve good glass wet-out. The resulting uncured mix is then cured under elevated temperature and pressure conditions as is well known to those skilled in the art. Upon cure, a polyurethane polymer product demonstrating desirable impact and strength properties is obtained.

The follwing examples are provided to further illustrate the invention. All parts are by weight unless otherwise specified.

PREPARATION OF POLYURETHANE OLIGOMER EXAMPLE 1

to 174 grams (2.0 eq.) of diisocyanate¹, 285 grams of styrene, 0.071 grams of hydroquinone and 0.142 grams of 2,6-di-tertiary-butyl-4-methylphenol (BHT) were added dropwise with stirring a mixture of 117.5 grams (0.8 eq.) of a polyether polyol², 19.2 grams (0.2 eq.) of a chain extender³, and 116 grams (1.0 eq.) of unsaturated monomer⁴ over a period of 2 hours. The reaction temperature rose from 21° to 36° C., and the mixture was stirred without heating for 2 hours after completion of the addition. At this point, 2.84 grams of catalyst⁵ were added. After stirring without heating for 15 minutes, the reaction mixture was heated to 70° C. and was stirred at 70° C. for 41/2 hours. The product had a viscosity of 5200 cps at 25° C.

EXAMPLES 2-10

Additional polyurethane oligomers were prepared employing the same conditions as in Example 1, except that the time was varied for the reaction at 70° C. in the final step of the procedure. Different reactants and proportions of reactants were also used. Table I outlines the oligomer compositions prepared according to Examples 2-10.

                                      TABLE I                                      __________________________________________________________________________     OLIGOMER COMPOSITIONS                                                                      Polyether Polyol                                                                        Chain Extender                                                                         Unsaturated Monomer                               Diisocyanate.sup.1                                                                         (eq.)    (eq.)   (eq.)      Viscosity                                                                             Reaction Time                   Example                                                                             (eq.)  A.sup.2                                                                            B.sup.3                                                                             C.sup.4                                                                            D.sup.5                                                                            E.sup.6                                                                            F.sup.7                                                                           G.sup.8                                                                            (cps at 25° C.)                                                                at 70° C.                __________________________________________________________________________                                                    (hrs.)                          1    2.0    0.8 --   0.2 --  1.0 -- --  5200   41/2                            2    2.0    --  0.6  0.4 --  --  1.0                                                                               --  4000   31/2                            3    2.0    --  0.2  0.6 0.2 0.5 0.5                                                                               --  640    4                               4    2.0    0.2 --   0.8 --  --  1.0                                                                               --  650    10                              5    2.0    0.6 --   0.2 0.2 --  1.0                                                                               --  3300   5                               6    2.0    0.8 --    0.15                                                                               0.05                                                                              0.5 0.5                                                                               --  5350   71/2                            7    2.0    0.1 0.1  --  0.8 --  1.0                                                                               --  350    61/2                            8    2.0    0.8 --   0.2 --  --  -- 1.0 355    51/2                            9    2.0    0.2 --   0.8 --  --  -- 1.0 500    7                               10   2.0    --  0.2  0.8 --  1.0 -- --  --     31/2                            __________________________________________________________________________      .sup.1 The diisocyanate is a mixture of toluene diisocyanate isomers           (80:20 mixture of 2,4/2,6isomers).                                             .sup.2 A polyether polyol having a molecular weight of about 650 and an        average functionality of about 4.25 and prepared by condensing a               sucrose/glycerol mixture with propylene oxide to a final hydroxyl number       of about 375.                                                                  .sup.3 A polyether polyol having a molecular weight of about 480 and an        average functionality of about 4.54 and prepared by condensing a               sucrose/glycerol mixture with propylene oxide to a final hydroxyl number       of about 530.                                                                  .sup.4 Tripropylene glycol.                                                    .sup.5 A polyether polyol having a molecular weight of about 425 and           prepared by condensing propylene glycol with propylene oxide to a final        hydroxyl number of about 265.                                                  .sup.6 Hydroxyethyl acrylate.                                                  .sup.7 Hydroxypropyl acrylate.                                                 .sup.8 Hydroxyethyl methacrylate.                                        

PREPARATION OF POLYURETHANE MOLDINGS EXAMPLES 11-16

Test panels were prepared containing polyurethane oligomers prepared according to Examples 2, 4∝7 and 10. The molding formulation used is listed in Table II below. The following procedure was followed in the preparation of the cured composites.

(a) Into a high shear mixing device were added to the polyurethane oligomer, sytrene, other monomers, catalyst and pigments.

(b) The filler was added gradually and mixed until a homogeneous paste was achieved.

(c) Next chopped fiberglass was added gradually to the paste in a two-roll mill and the mix was worked the minimal length of time to achieve good wet out of the glass without significant breakdown.

(d) The uncured mix was then placed in a mold between the platens of a compression molding machine and cured under pressure (2,000 psi) for three minutes at 300°-325° F.

(d) Alternatively to (d), the mixture may be added by a hopper device to the screw system of an injection molding device to produce an injection molded part, or the mix may be made up on an SMC machine for later compression or injection molding.

The physical properties of panels prepared in this manner are included in Table III below. The physical properties were determined in accordance with standard test procedures: Flexural modulus and flexural strength--ASTM D790; tensle strength and elongation--ASTM D3574; and falling dart impact--ASTM D3029.

                  TABLE II                                                         ______________________________________                                         POLYURETHANE MOLDING FORMULATION (BMC)                                         Component           Parts by Weight                                            ______________________________________                                         Polyurethane Oligomer                                                                              100    (40% Styrene)                                       Tertiary Butyl Perbenzoate                                                                         1.4                                                        Tertiary Butyl Peroctoate.sup.1                                                                    0.5                                                        Zinc Stearate       4.3                                                        Calcium Carbonate   160                                                        1/2 Inch Glass      99                                                         ______________________________________                                          .sup.1 Commercially available from Lupersol Co. under the designation          "PDO", understood to consist of 50% tertiary butyl peroctoate and 50%          dioctyl phthalate.                                                       

COMPARATIVE EXAMPLE 1

For purposes of comparison, a test panel containing a polyester resin was prepared following the procedure of Examples 11-16. The molding formulation employed was as follows:

    ______________________________________                                         Component           Parts by Weight                                            ______________________________________                                         Polyester Resin.sup.1                                                                              100    (36% Styrene)                                       Tertiary Butyl Perbenzoate                                                                         1.4                                                        Tertiary Butyl Peroctoate.sup.2                                                                    0.5                                                        Zinc Stearate       4.3                                                        Calcium Carbonate   160                                                        1/2 Inch Glass      99                                                         ______________________________________                                          .sup.1 A vinyl ester resin commercially available from Dow Chemical            Company under the designation "Derakane 470".                                  .sup.2 Commercially available from Lupersol Co. under the designation          "PDO", understood to consist of 50% tertiary butyl peroctoate and 50%          diocytl phthalate.                                                       

The physical properties of the panel prepared in this manner are included in Table III below. The physical properties were determined in accordance with standard test procedures: Flexural modulus and flexural strength--ASTM D790; tensile strength and elongation--ASTM D3574; and falling dart impact--ASTM D3029.

In comparing the results, the composites prepared from polyurethane oligomers of the invention showed overall properties generally improved over those demonstrated by the composite made from the conventional vinyl ester. These composites exhibited desirable impact properties, and enhanced flexural strength and modulus, the latter characteristics indicating improved strength, which is particularly important for automotive body applications.

                                      TABLE III                                    __________________________________________________________________________     PHYSICAL PROPERTIES OF POLYURETHANE OLIGOMER COMPOSITES                                                                               Falling Dart                              Tensile Strength                                                                        Flexural Strength                                                                       Flexural Modulus × 10.sup.6                                                           Elongation                                                                           Impact                  Example                                                                             Polyurethane Oligomer                                                                       (psi)    (psi)    (psi)        (%)   (in.-lb.)               __________________________________________________________________________     11   Example 2    5500     12,700   1.10         1.63  24                      12   Example 4    3950     14,600   1.28         1.26  30                      13   Example 5    5500     14,100   1.18         1.46  27                      14   Example 6    3950     12,300   1.18         1.37  30                      15   Example 7    4750     14,600   1.22         1.33  27                      16    Example 10  5230     13,800   1.11         1.47  29                      CE-1 --           4700     10,500   0.98         1.16  27                      __________________________________________________________________________ 

What is claimed is:
 1. A process for preparing a polyurethane polymer product comprising mixing a polyurethane oligomer, a heat activated free radical generating catalyst, and at least one additional component selected from a reinforcing agent and a filler to a homogeneous blend, and then heating said mixture at a temperature adequate to activate said catalyst and cure said mixture, said polyurethane oligomer having an equivalent ratio of NCO to OH from about 0.8/1 to about 2/1 and being prepared by reacting(a) an organic polyisocyanate; (b) a polyol reactant comprising(i) a high functionality polyol having an average equivalent weight from about 75 to about 500 and an average functionality of at least about 3, said high functionality polyol being prepared by reacting an alkylene oxide, or a mixture of alkylene oxides, with a polyhydric initiator comprising a carbohydrate or a carbohydrate derivative, and (ii) a chain extender having an average equivalent weight from about 31 to about 4,000 and an average functionality of about 2, said chain extender being employed in an amount ranging from about 20 to about 1,500 parts by weight per 100 parts by weight of said high functionality polyol; and (c) an isocyanate reactive group-containing unsaturated monomer selected from the group consisting of(i) hydroxyalkyl acrylates, (ii) hydroxyalkyl methacrylates, (iii) hydroxyalkyl acrylamides, and (iv) mixtures thereof; and wherein there is employed an equivalent ratio of said isocyanate reactive group-containing unsaturated monomer to said polyol reactant in the range from about 0.6/1 to about 3/1.
 2. The process of claim 1, wherein:said high functionality polyol has an average equivalent weight of about 75 to about 350, said polyurethane oligomer has an equivalent ratio of NCO to OH from about 1/1 to about 1.2/1, and said equivalent ratio of said isocyanate reactive group-containing unsaturated monomer to said polyol is in the range from about 0.8/1 to about 2/1.
 3. The process of claim 2, wherein said reaction is carried out in the presence of a copolymerizable solvent.
 4. The process of claim 3, including adding to said mixture, per 100 parts by weight of said polyurethane oligomer, from about 100 to about 220 parts by weight of a filler and from about 60 to about 130 parts by weight of a reinforcing agent.
 5. The process of claim 4, wherein said high functionality polyol has an average equivalent weight of about 90 to about 200 and an average functionality of about 3.3 to about 6 and is prepared by reacting a polyhydric initiator selected from mixtures of sucrose, dextrose or methyl glucoside and an aliphatic triol with an alkylene oxide selected from propylene oxide and mixtures of propylene oxide and ethylene oxide.
 6. The process of claim 5, wherein said chain extending agent is selected from the group consisting of tripropylene glycol, polyether diols having an equivalent weight of about 100 to about 500, and mixtures thereof.
 7. The process of claim 6, wherein said unsaturated monomer is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and mixtures thereof.
 8. The process of claim 7, wherein said copolymerizable solvent is styrene.
 9. The process of claim 8, wherein said heat activated free radical generating catalyst is a peroxide catalyst.
 10. The process of claim 9, wherein said peroxide catalyst is selected from t-butyl perbenzoate, t-butyl peroctoate, and mixtures thereof, and said organic polyisocyanate is toluene diisocyanate.
 11. The process of claim 10, wherein said reaction is accelerated by employing a urethane catalyst.
 12. The polyurethane polymer product prepared according to the process of claim
 1. 13. The polyurethane polymer product prepared according to the process of claim
 2. 14. The polyurethane polymer product prepared according to the process of claim
 3. 15. The polyurethane polymer product prepared according to the process of claim
 4. 16. The polyurethane polymer product prepared according to the process of claim
 7. 17. The polyurethane polymer product prepared according to the process of claim
 11. 